Esters of chloralmonofluoracetamides



United States Patent 3,234,24s ESTERS 0F CHLORALMQNOFLUORACETAMlDEd Otto Scherer, Frankfurt am. Main, and Hans Hahicht, Kelkheim, Taunus, Germany, assignors to Farbwerlre Hoecbst Aktiengesellschaft vormals Meister Lucius & Briining, Frankfurt am Main, Germany, a corporation of Germany No Drawing. Filed Mar. 5, 1963, Ser. No. 262,824 Claims priority, application Germany, June 24, 1961,

11 Claims. (Cl. 260404) in which R is a saturated or monoolefinic unsaturated alkyl radical having 17 C-atoms, which may also be substituted by halogen or the SC H group, or an aryl radical are equally active as systematic insecticides and contact insecticides and acaricides, but are considerably less toxic towards warm-blooded animals than the known compounds.

In order to be made up into pulverulent or liquid prepin the form of a gas and may be bound, for example, with the aid of a tertiary base.

If no base is used, the O-acyl-compounds formed can directly be subjected to distillation under reduced pressure after removal of any solvent. If a base is used the O-acyl-compounds formed can be distilled under reduced pressure after filtration from the salt, subsequent washing and drying of the filtrate and removal of any solvent.

The reaction may also be carried out with the corresponding acid anhydride instead of the acid chloride.

The Ofacyl derivatives so produced constitute colorless, sirupy, wax like or crystalline substances, which can be easily purified by distillation or recrystallization. They are thermostable and, provided the pressure is sulficiently reduced, they withstand distillation at temperatures of up to 180 C. without decomposition.

The corresponding not acylated ooinpo unds cannotbe distilled without decompositiongthey decompose already at much lower temperatures and with extensive formation of chloral.

in the following table, some of the new compounds are compared with the known fiuoracetamide; In column l are indicated the designations of the compounds, in column 2 are given their boiling points and the respective pressures, in column 3 are given the melting points, and in column 4 the. LD IMO. in mg. of active substance per. kg. of rat (albino rats). In column 5 are listed in the values of molar toxicity, obtained by division of the LD of column 4 by the corresponding molecular weight. The LD values indicated are all higher than arations suitable for use, the active substances of the the corresponding value of monofluoracetamide.

TABLE Compound. ggi g Melting LD Molar mIn. point, *0. LB

O-diniethylacrylyl-chloralmonofluoracetalnide ,Q c. 146447/2. 5 50-54 -90 0. 26-0. 29 O-acetyl-chlora lmonofiuoracetamide. 124-126/1. 2 :97 80-90 0. 30-0. ,34 O-propionyLchloralmonofluoracetamide. 135-13715 48-50 O. 36 O-n-butyryl-ehloralmonofiuoracetamide 140142l5 70-72 170-200 0. 58-0. 68 O-i-butyryl-chloralmonotluoracetamide- 124-125/0. 5 63-66 150200 0. 51-0. 68 O-heuzoyl-ehloralmonofluoracetarnide 98-100 135 0. =11 O-cr0tonyl-chloralmonofluoracetamlde 135-140/0. 4 45 0.16 On-caprylyl-chlornltluoracetamide 146150/1. 5 Oil 135 0. 39 O=2 chloro-propionyl-chloralfiuoracctamide 144-14810. 2 65 0. 21 O-(ethyl-mercapto)-acctyl-ehloralfiuoracetainide 153155/3. 0 Oil 70 0. 22

Monoiluoracetamide /52 108 15 0. 19

1 Oil, solidifies.

present invention can be admixed with any of the auxiliary agents conventionally used for such purposes in this field. For example, they can be made up with wetting agents into'so-called wettable powders which are then transformed into spray solutions shortly before use. More particularly, the invention relates to the use of O-acetyl-chloralmonofiuoracetamide and the analogous O-propionyl-, O-n-butyryL, Oi-butyryl-, 0-eaprylyl-, O-crotonyl-, O-dirnethylacrylyl-, O-benzoyl-, O-(ethylmercapto -acetyland O- (Z-chloropropionyl -derivatives which correspond to the above-indicated formula.

The compounds to be used in accordance with the present invention can be obtained, for example, from the corresponding chloralmonofluoracetamide, which had been prepared in the usual manner, when exposing this compound to the action of the corresponding acid chloride. The reaction may be carried out in the presence of a solvent. As such a solvent there may be used one of the conventional solvents, for example, toluene, benzene, or petrol ether. The reaction is carried out at a temperature in the range of 50-150 (3., preferably 100- C. The hydrochloric acid that forms thereby escapes The following examples illustrate the invention, but they are not intended to limit it thereto:

Example 1 224.5 g. (1 mol) of chloralfiuoracetamide, g. (1.2 mol) of dimethylacrylic acid chloride and 200 cc. of toluene are refluxed, which proceeds at about 120 C., for so long until the quantity of escaping hydrogen chloride gas is but small. This requires approximately 3 hours. After having removed the toluene and the excess acid chloride by distillation under reduced pressure, the remaining oil is also subjected to distillation.

The product of the invention passes over at a temperature in the range of 148150 C. and a pressure of 1.5 mm. Hg in the form of a colorless sirup which solidifies after a short time to yield a wax-like mass. 246 g. (80% of the theoretical yield) are thus obtained.

Example 2 Larvae of ticks of the genus Ornithodorus moubata, which were placed in glass dishes coated with filter paper that had been sprayed with 1.5 cc. of a spray liquor coning 1.2%

taining 0.3% of Q-climethylacrylyl-chloralmonofluoracetamide as the active substance, died after a few hours.

Example 3 Example 4 Plants of the variety Vicia faba infested with plant-lice of the genus Doralis fabae were sprayed with an aqueous solution of 0.4% strength of a preparation consisting of 30% of O-dimethylacrylyl-chloralmonofluoracetamide, 50% of cyclohexanone, and 20% of nonylphenol; this treatment killed all the plant-lice.

Example 5 The same effect on plant-lice was produced when using instead of O-dimethylacrylyl-chloralmonofluoracetamide one of the following derivatives:

O-crotonyl-chloralmonofluoracetamide O-acetyl-chloralmonofiuoracetamide O-propionyl-chloralmonofluoracetarnide O-n-butyryl-chloralmonofluoracetamide O-i-butyryl-chloralmonofluoracetamide O-benzoyl-chloralmonofluoracetamide.

Example 6 Example 7 p a Polyester fibres that had been cut to short pieces were placed in a glass dish and the dish was then sprayed with 1.5 cc. of a spray liquor containing 0.4% of O-acetylchloralmonofluoracetaniide. After the sprayed liquor had dried, older larvae of ticks were placed into the dish,

at a temperature of +35 C. All of these larvae were destroyed after a few days.

Example 8 The same effect on ticks could be produced with O-isobutyryl-chloralmonofluoracetamide as the active substance.

Example 9 Example 10 When plants of the variety Vicia faba infested with plant-lice of the genus Doralis fabae were sprayed with an aqueous solution of 0.1% strength of a preparation consisting of 15% of O-(ethyl-mercapto)-acetyl-chl0ralmonofiuoracetamide as the active substance and, as inert substances, 64% of active silicic acid, 10% of cell pitch and 1% of oleic acid methyl tauride, all plant-lice were killed already after a few hours.

The same compound with the above formulation, but applied at an application rate of 0.7% of formulated product, proved very active against ticks of the genus Ornithoa'aras moubata which were all killed.

Example 11 The same effect against plant-lice as describedin EX- arnple 10 Was obtained with a 0.05% dilution of a preparation containing 15% of O-2-chloropropionyl-mono fiuoracetamide as the active substance.

For killing ticks of the genus Ornithodoras moabata, the corresponding application rate of the same formulation was 1.2%.

Example 12 The systemical insecticidal properties of O-crotonylchloral-monofluoracetamide or of O-n-caprylyl-chloralmonofluoracetamide could be proved by the following tests:

Stems of plants of the variety Vicia faba infested with plant-lice were provided at their lower part with a bandage of cotton-wool and covered with cellulose glass; the cotton-wool containing 1 mg. of the respective active substance in fine distribution. All the plant-lice sucking on the upper parts of the plants were killed within 3 days by each of the above-indicated compounds.

We claim:

1. Compounds of the formula CEzFCO-NHCHOGR (IJCM O in which R is a member of the group consisting of saturated and monoolefinic alkyl groups having l7 C-atoms and their chlorine and SC H substituted derivatives, and phenyl.

.. O-dimet-hylacrylyl-chloralrnonofluoracetamide.

. O-acetyl-chloralmonofluoracetamide.

. O-propionyl-chloralmonofiuoracetamide.

O-n-butyryl-chloralmonofluoracetamide.

. O-ibutyryl-chloralmonofluoracetamide.

. O-benzoyl-chloralrnonofluoracetamide.

. O-crotonyl-chloralmonofluoracetamide.

. O-n-caprylyl-chloralfluoracetamide.

10. O-2-chloropropionyl-chloralfiuoracetamide.

11. O- ethyl-mercapto -acetyl-chloralfiuoracetamide.

- References Cited by the Examiner UNITED STATES PATENTS 2,268,206 12/1941 Epstein et al 260-404 X 2,357,078 8/1944 Brown 167-22 2,477,346 7/1949 Pik 260404 2,514,376 7/1950 Crooks 260490 2,831,018 4/1958 Trieschmann et al. 260490 2,834,792 5/1958 Wilkinson et al. 260-490 2,898,265 8/1959 Wegler 167-30 CHARLES B. PARKER, Primary Examiner. 

1. COMPOUNDS OF THE FORMULA 